Pebble heater



Dec. 16, 1947.

B. J. ERRQ, JR raanu manna F1106. Oct. 21. 1946 2 Sheets-Sheet l uvewron a. J. FERRO, JR. M" i/ ATTORNEYS Dec. 16, 1,947.

B. J. FERRO, JR

PEBBLE HEATER 2 Sheets-Sheet 2 Filnd Oct. 21,- 1946 TEMPERATURE FIG 3 72138.15 .40 AcF'IVHLNH 'IVLOJ.

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TEMPERATURE FIG. 2

INVENTOR B. J. FERRO. JR.

ATTORNEYS Patented Dec. 16, 1947 PEBBLE HEATER Bernardo J. Ferro, Jr., Bartlesville. kla., assignor to Phillips Petroleum Company, a corporation of Delaware Application October 21, 1946, Serial No. 704,694

7 Claims. (Cl. 196-55) This invention pertains to an improved process and apparatus for heating gases by contact with a descending stream of hot pebbles. A specific aspect of the invention relates to a process and apparatus for high temperature conversion of hydrocarbons.-

Pebble heater operation with which this inven-- tion is concerned is being utilized in a variety of chemical processes and treatments in which extremely fast heating of the gas is required. Its application includes conversion of hydrocarbons at high temperatures, such as cracking and dehydrogenation, the synthesis of HCN from NH: and CO, the synthesis of CS2 by reacting hydrocarbon vapors with sulfur containing gases, etc. Conventional pebble heater technique entails circulating a continuous mass of pebbles by gravity through a series of chambers or zones, elevating them to a point above the upper chamber, and again allowing them to descend by gravity through the several chambers. In a typical hy-. drocarbon conversion process pebbles are heated in an upper chamber by contact with a countercurrent stream of hot flue gas after which they pass into a conversion chamber where they heat the hydrocarbons being processed and supply the heat of reaction required. In many installations a third chamber is positioned below the conversion chamber to effect the preheating of the feed stock. Pebbles emerging from this third Zone are sufficiently cool to be handled in ordinary carbon steel elevator equipment. In some processes, instead of preheating the feed in the third chamber, air or fuel for combustion purposes in connection with the pebble heating chamber are circulated through the lower chamber to be preheated and to cool pebbles therein. It is in pebble heater operation involving a gas preheating step in a third chamber with which this invention is concerned.

In processes in which the fluid stream being treated undergoes a physical or chemical reac-' tion accompanied by an appreciable change of specific heat. some diificulty is encountered in regulating and controlling the temperature differential between the pebble and fluid stream. The same difliculty is encountered when there is a large difference between the specific heats of the fluid and pebble stream. In endothermic reactions, e. g., the differential between inlet pebble temperature and outlet gas temperature in the reaction chamber must be relatively high in order to transfer suflicient heat to the reaction cham- -ber to effect the process desired. It is also desirable that there be substantial difference between outlet pebble temperature and inlet gas temperature. This means that the pebbles entering the preheating chamber are at a relatively high temperature and, since the volume of gas being preheated is the same as that being reacted, the heat exchange between the pebble stream and the fluid stream in the preheating chamberedoes not lower pebble temperature to the proximity of inlet gas temperature. This means a relatively high differential between gas inlet temperature and pebble outlet temperature in the preheating chamber. Such high differential between pebble and fluid temperatures resuits in large superficial thermal stresses and subsequent breaking of pebbles. It also results in less efllcientutilization of heat in pebble heater operation. It is with these diiliculties that the present invention is concerned.

It is an object of the present invention to provide a means for regulating and controlling the temperature approach or difference between the pebble and fluid stream in a pebble heater where the latter stream undergoes a physical or chem ical reaction accompanied by an appreciable change of specific heat or where there are large differences betweenthe specific heat of the fluid and pebble stream. It is also an object of the invention to reduce or eliminate pebble breakage in pebble heater operation. A further object of the invention is to provide for more efilcient operation of a pebble heater by permitting closer correlation between pebble and fluid stream temperatures. It is also an object of the invention to prevent temperature lock of the two streams and at the same time prevent extremely large temperature differences either at the top or bottom of the heater.

The term pebble as referred to throughout the specification is defined as any particulate refractory contact material which is readily flowable through a contact chamber. Pebbles are preferably spherical in form, and range from about A; inch to 1 inch in size, but spheres ranging in size from about inch to /2 inch are the most practical. Uniform shapes and sizes are preferred but pebbles oi irregular shape and size may be used. Pebbles may be made or ceramic matelilal such as alumina or of metals and alloys such as iron, nickel, monel andJnconel.

While the invention has its greatest applicability in the conversion of hydrocarbons it is not so limited but is applicable to any pebble heater proce s enhanced by careful control of pebble and fluid temperature diilerentials.

The invention provides for the removal. of a separate stream of pebbles from the main pebble stream near the bottom of the reaction c amber and transfer of this separate pebble stream to the pebble heating c amber. Thus. by permitting only a portion of the pebble stream to flow through the preheating chamber, the diflerential between feed inlet temperature and pebble outlet temperature in the preheating chamber may be accurately controlled in a low range. The volume of the pebble stream removed from the bottom of the reaction chamber is controlled in accordance with a predetermined temperature ditferentlal between pebble outlet temperature and feed gas inlet temperature in the preheating zone. Flow of the main ebble stream is regulated in response to the different al between teed inlet temperature and pebble outlet temperature in the conversion or reaction zone.

In order to facilitate understanding of the invention reference is made to the drawing 01' which Figure 1 is an elevational view partly in section of a preferred arrangement of apparatus according tothe invention. Figure 2 is a graphic representation oi the relation between the temperature and total enthal y of a pebble and fluid stream in a typical pebble heater hydrocarbon cracking process without stepwise removal of pebbles. Figure 3 is a raph c repre entation of the temperature-enthalpy relation of' the same two streams, but with removal of a portion of the pebble stream a ter the cracking operation takes place and before the pebble stream descends into the preheating zone.

Referring to Figural, numerals ll, i2 and I3 designate a pebble hea i g chamber. a as treating or conversion chamber. and a gas preheating L into the chamber through line 36 and egressing through line 31. The hot pebble stream entering conversion chamber I2 s contacted bv pre eated gas entering the chamber through line 39 and supplies the heat requirements of the proce s in this chamber. -Eilluent products from chamber l2 are taken off through line 4| which leads to treating apparatus not s own. During passage of the partially cooled pebbles through preheating chamber I3 they are contacted in counter current flow with a stream of feed gas admitted through line 38 and taken off through line 39 which leads into chamber l2, The relatively cool pebble stream is taken off through line 20 and chute 2| which leads to elevator 22. Elevator 22 lifts the pebbles to a point above heating chamber II and drops them into chute 23 from which they are delivered into pebble inlet l6 and again flow into the heating chamber,

4 Outlet I8 and chute 24 serve to withdraw a separate stream of pebbles from the lower part of reactor l2. Elevator 25 hits this stream of pebbles to a point above heating chamber H and drops them into chute 28 from which they flow through inlet ll into heating chamber H. Pebble inlet I! is preferably extended into the heating chamber to a point at which the pebble temperature is approximately that or the separate stream or pebbles being introduced. Throats M and i5 and pebble inlet l6 extend into their respective chambers a short distance in order to provide a small vapor space above the pebble bed which has a conical top 43 in each of the chambers. Pebble throats and chambers are retractory lined and the latter are advantageously constructed with conical bottoms which serve as hoppers to feed the pebbles out or their respective chambers.

One of the important'features of the invention is the control of temperature in the conversion zone through the regulation of temperature difierential between points 5 and 6 therein and control of temperature differential in the preheating chamber between points I and 8. The rate of flow of the main pebble stream is regulated by variable speed motor 21 which is operated by temperature controller-recorder 28 in response to variations from a predetermined temperature differential between points 5 and 6 in reaction chamber i2. Thermocouples 29 and 3| located at points 5 and 6 respectively, register the temperature of the incoming preheated feed at point 5 and the temperature of the outgoing pebbles at point 6. When the temperature difi'erential between points 5 and 6 becomes too high, temperature controller-recorder 28 slows down the speed of motor 21 which immediately decreases the flow rate of pebbles through reactor I2 and consequently reduces the temperature differential between points 5 and 5.

In order to maintain a predetermined temperature differential between points i and 8 in preheater l3 and thereby reduce thermal shock to the pebble stream, a separate stream of pebbles is withdrawn from the main stream at point 6 in reactor i2 and is conveyed through outlet i8 and chute 24 into elevator 25. The flow of this separate stream is controlled .by variable speed motor 32 which is responsive to temperature controller-recorder 33 connected to thermocouple 34 and 35 located at points 1 and 8, respectively. Any variation in a predetermined differential between points 1 and 8 is reflected in a change in the speed of motor 32 and therefore in the rate at which pebbles are withdrawn from the main stream at point 6. By changing the rate at which this separate stream of pebbles is withdrawn from the main stream the available heat of the pebble stream passing through the preheating chamber can be controlled along with the differential between the temperature of the pebbles at point i and the temperature of the feed coming in at point 8. Any increase in the flow rate of the auxiliary pebble stream taken off at point 6 will tend to increase the differential between temperatures at points 5 and 6 because of the resulting increase in the flow of pebbles into chamber it. However, any increase in the diiferential between the temperatures at point 5 and 6 is immediately translated into a slower movement of the main pebble stream through control of motor 21. Likewise any increase in flow of the main pebble stream to maintain a predetermined temperature differential between points 5 and 6 will tend to raise the temperature diiferential between points 1 and B in preheating chamber 13. This tendency is immediately offset by an increase in flow of pebbles through the auxiliary stream. It can readily be seen that the controls described are correlated to maintain predetermined temperature diiferentials at points 5 and 6 and at points '1 and 8.

Other arrangements of the apparatus shown are feasible. Some installations utilize a single long chamber having a pebble heating zone in the upper end, a feed preheating zone in the lower end, and a conversion zone intermediate thereof. In such a system, intermixing of gases is prevented to a large extent by proper control of pressures, The temperature control system of the invention is also applicable to this type of pebble heater installation.

Certain modifications in the temperature control system are feasible. Temperature controllerrecorder 28 may be connected to a valve in throat 14 between chambers H and I2 thereby regulate the main flow of pebbles into chamber 12. Likewise temperature controller-recorder 33 may connect to a valve or pebble feeder device in chute 24. However, control of pebble flow by variable speed conveyer drivers is preferred.

The system shown in Figure 1 operates most advantageously at gas pressures of .5 to 6 p. s. i. g.,

but other pressures above and below atmospheric may be utilized. In order to prevent escape of gases to various chambers steam lines 44, 45, 46,

41, 48 and 49 may be utilized to form a steam block in the zones to which they lead, Other non-deleterious gases may be introduced through these lines to prevent mixing of feed and combustion gases.

The graphs of Figures 2 and 3 clearly illustrate the advantage in temperature control obtained by operating according to the invention. Temperature-enthalpy lines are shown for both hydrocarbon and pebble streams in a typical hydrocarbon cracking operation. Figure 2 represents operation in which there is no step-wise withdrawal of pebbles. while Figures 3 represents operation where pebbles are withdrawn in a separate stream from the lower portion of the conversion chamher. In F gure 2. the temperature-enthalpy line of the pebble stream is shown as AB, and that for the hydrocarbon as CD. An initial temperature difference AT-e is selected so that a desirable ATf is obtained at the beginning of the cracking reaction. It is apparent that this results in a larger AT-g than is required for eflicient preheating of the feed and produces undue thermal strain on the exterior surface of the pebbles.

In Figure 3, line 9--58 represents the temperature-enthalpy relation of the fluid stream as it passes from point 8 to point 5 to point 9 in the system shown in Figure 1. Line 4-G1 represents the temperature-enthalpy relation of the pebble stream in its passage from point 4 through point 6, to point I of Figure 1. A side stream of pebbles is withdrawn at point 6. AT(4-9) is the same as ATe, and AT(65) is the same as ATf; but it can be readily seen that AT(l-8) is considerably smaller than AT-g. In other words, utilizing the same differential between pebble inlet temperature and product outlet temperature from the reaction zone and the same temperature differential between inlet feed gas and outlet pebble temperature in the reaction zone, the invention makes it possible to operate with a much lower temperature differential between the pebble and fluid stream in the lower portion of the preheating chamber. This feature of my invention permits better utilization of heat and less pebble breakage than is obtained in conventional operation.

In a typical utilization of my invention, a feed stock having the following composition by weight per cent:

Methane 2.6 Ethane 21.6 Propane 74.5 Butanes and heavier 1.3

is processed in apparatus arranged according to Figure 1 to produce an olefin-rich gasof the following composition by weight percent;

Hydrogen 2.1 Methane 21.0 Ethylene 36.5 Ethane 13.4

Propylene 9.4 Propane 7.7 Butanes and heavier 9.9

under the following temperature conditions:

Feed at 8 (Figure 1) Feed preheat at 5 1,200 Product at 9 1,700 Gas entering line 36 3,600 Flue gas, line 31 600 Pebbles at 4.... 1,900 Pebbles at 6 1,400 Pebbles at 1 400 A relatively constant feed rate of 68 625 cu. ft. per hour is maintained with a production of 122,917 cu. ft. of .product gas using inch dense high purity alumina pebbles. The main pebble stream at point 6 is divided, a side stream being taken off and reintroduced in pebble heater II at a temperature point approximately that of the pebbles being introduced. Pebble flow in the two streams is regulated automatically by controls 28 and 33 to maintain relatively uniform temperature differentials of 200 F. between points 5 and 6 and 300 F. between points I and 8. Pebble breakage due to thermal stresses is considerably reduced over pebble breakage resulting from operation in which higher differentials obtain.

It can readily be seen that my invention results in more efficient utilization of heat than is obtained in conventional pebble heater operation, with less thermal shock and physical strain on the pebbles.

Operation according to the invention is not limited to the specific temperatures recited in the example. Conversion temperatures may be varied from about 1300 to about 3000 F with correspondingly varied pebble temperatures. Temperature differentials between the gases being processed and pebbles may likewise be varied to suit the particular type of process involved. When highly endothermic reactions are being conducted in the conversion chamber temperature differential therein between pebbles entering and prod-- ucts leaving the chamber is desirably higher and may be of the order of about 500 to about 600 F. In processes requiring slower rates of heat transfer temperature differentials may be as low as 100 F.

Various modifications of the invention will become apparent to those skilled in the art. The illustrative details disclosed are not to be construed asimposing unnecessary limitations on the invention.

I claim:

1. A continuous process for efiectlng thermal reactions at elevated temperatures in the vapor phase which comprises continuously flowing by gravity a contiguous fluent mass of hot refractory pebbles through a, series of substantially vertically extending zones comprising from highest to lowest a pebble heating zone, a reaction zone, and a feed preheating zone, and several relatively narrow connecting zones for permitting free flow of pebbles between said first-named zones, all of said zones being substantially filled with said pebbles; continuously contacting that portion of said mass of pebbles in said pebble heating zone with a stream of hot combustion gas, thereby heating said pebbles to a temperature substantially above a predetermined reaction temperature; continuously contacting that portion of said mass of pebbles in said pre-heating zone with a stream of feed gas to be reacted, thereby preheating said gas a substantial amount; continuously passing the thus preheated feed gas into said reaction zone and there contacting that portion of said mass or pebbles in said zone with said preheated feed gas, thereby heating and reacting said feed gas a controlled amount; continuously transferring pebbles from the lower portion of said preheating zone to the upper portion of said pebble heating zone at a, rate controlled to maintain a predetermined temperature differential between the inlet gas temperature and outlet pebble temperature in the reaction zone, thereby maintaining a predetermined reaction temperature; simultaneously withdrawing pebbles from the lower portion of said reaction zone at a rate controlled to maintain a predetermined temperature diiferen tial between feed gas inlet temperature and pebble outlet temperature in the preheating zone; introducing the pebbles thus withdrawn to the pebble heating zone at a, temperature point in the pebble stream therein substantially that of the pebbles being introduced; and continuously recovering eilluente from the reaction zone.

2. A continuous process for effecting conversion of hydrocarbons in the vapor phase which comprises continuously flowing by gravity a contiguous fluent mass of hot refractory pebbles through a series of substantially vertically extending zones comprising from highest to lowest a pebble heating zone, a conversion zone, and a hydrocarbon preheating zone, and several relatively narrow connecting zones for effecting relatively free flow of pebbles between said first-named zones, all of said zones being substantially filled with said pebbles; continuously contacting that portion of said mass of pebbles in said pebble heating zone with a stream of hotcombustion gas thereby heating said pebbles to a temperature substantially above a predetermined conversion temperature; continuously contacting that portion of said mass of pebbles in said reheating zone with a hydrocarbon vapor stream to be converted, thereby preheating said hydrocarbon stream a substantial amount; continuously passing the thus preheated hydrocarbon stream into said conversion zone and there counter-currently contacting that portion of said mass of pebbles in said zone with said preheated hydrocarbon stream thereby effecting desirable conversion of said hydrocarbons; continuously transferring pebbles from the lower portion of said preheating zone to the upper portion of said pebble heating zone at a rate regulated to maintain a predetermined temperature differential between inlet vapor temperature and outlet pebble temperature in the conversion zone thereby maintaining a, predetermined conversion temperature: continuously withdrawing pebbles from the lower portion of said conversion zone in a separate stream at a rate regulated to maintain a predetermined temperature differential between hydrocarbon inlet temperature and pebble outlet temperature in the preheating zone and introducing the pebbles thus withdrawn to the pebble heat. ing zone at a, point in the pebble stream therein at which the temperature is approximately the temperature of th pebbles being there introduced; and continuously recovering eiiiuents from the conversion zone.

3. A continuous process for eifecting thermal treatment of gases at elevated temperatures which comprises continuously flowing by gravity 9. fluent mass of hot refractory pebbles through a series of substantially vertically extending zones comprising from highest to lowest a pebble heating zone, a gas treating zone, and a gas preheating zone; continuously contacting that portion of said mass of pebbles in said pebble heating zone, with a stream of hot combustion gas, thereby substantially heating said pebbles; continuously contacting that portion of said mass of pebbles in said preheating zone with a countercurrent stream of the gas to be treated, thereby preheating said gas a substantial amount; continuously contacting that portion of said mass of pebbles in said treating zone with a countercurrent stream of the thus preheated gas, thereby effecting the desired treatment of'said gas; continuously transferring pebbles from the lower portion of said preheating zone to the upper portion of said pebble heating zone at a rate regulated to maintain a predetermined temperature differential between inlet gas temperature and outlet pebble temperature in the gas treating zone, thereby maintaining a predetermined gas treating temperature; continuously withdrawing pebbles from the, lower portion of said gas treating zone in a separate stream at a, rate regulated to maintain a predetermined temperature differential between gas inlet temperature and pebble outlet temperature in the preheating zone and introducing the pebbles thus withdrawn to the pebble heating zone; and continuously recovering eiiiuents from the gas treating zone.

4. A continuous process for cracking hydrocarbons at elevated temperatures in gas or vapor phase which comprises continuously flowing by gravity a contiguous fluent mass of hot refractory pebbles through a series of substantially vertically extending zones comprising from highest to lowest a. pebble heating zone, a cracking zone, and a, hydrocarbon preheating zone each substantially filled with said pebbles; continuously contacting that portion of said mass of pebbles in said pebble heating zone with a stream of hot combustion gas, thereby heating said pebbles to a temperature substantially above a predetermined cracking temperature; continuously contacting that portion of said mass of pebbles in said preheating zone with a stream of hydrocarbon gas to be cracked, thereby preheating said stream a substantial amount; continuously passing the thus preheated hydrocarbon stream into said cracking zone in contact with that portion of said mass of pebbles therein, thereby heating and cracking said hydrocarbon stream a controlled amount; maintaining said predetermined cracking temperature in said cracking zone by continuously withdrawing pebbles from the lower portion of said preheating zone at a rate responsive to variations in temperature differential between inlet gas temperature and outlet pebble temperature in said cracking zone; maintaining a predetermined temperature difierential between inlet gas and outlet pebbles in the preheating zone by removing a separate stream of pebbles from the lower portion of the cracking zone at a rate responsive to variations from said predetermined temperature difiential; and continuously recovering chamber for heating pebbles with heat of fuel combustion; supply and discharge'means leading to and from said heating chamber for flow of fuel thereto and combustion gas therefrom; a conversion chamber for converting hydrocarbons to desired products disposed at a lower level than said pebble heating chamber; supply and discharge means leading to and from said conversion chamber for flow of hydrocarbons thereto and conversion products therefrom; a hydrocarbon preheating chamber disposed at a lower level than said conversion chamber; supply and discharge means leading to and from said preheating chamber for flow of cool hydrocarbons there.- to and preheated hydrocarbons therefrom, said discharge-means being in communication with the supply'means to said conversion chamber; conduit means connecting the several chambers for flow of pebbles from the highest to the lowest chamber in series; pebble outlet means in the lower portion of said preheating chamber and pebble inlet means in the upper portion of said heating chamber; means for transferring pebbles from said pebble outlet means to said pebble inlet means; means for actuating said pebble transferring means at variable rates responsive to temperature differential between selected points in said conversion chamber; pebble outlet means in the lower portion of said conversion chamber for removing a separate stream of pebbles from the main stream; pebble inlet means. for introducing said separate pebble stream into the upper portion of said heating chamber; means for transferring said separate'pebble stream from said last-named pebble outlet means to said lastnamed pebble inlet means; and means for actuating said last-named pebble transferring means at variable rates responsive to temperature differential between selected points in said preheating chamber.

. BERNARDQ J. FERRC, JR.

REFERENCES CITED The following references are of record in the Wolk Oct. 23, 1945 

